Mineral oil



Pate'nted May 12, 1953 I STATES aessn is; I

MINERALUE" Joseph J. Welinle, Glarksbom,l-,N: J., a;ssign0ri toSocony-Vacuumflii Company, ln'tbmratefl;=' .a. corporation of New Yorkreclai s.- (mesa-46.1.)-

This: invention relates; broadly, to lubricants and it is'fmoreparticularly 'concernedvwith: mineral; an improved antioxidant. 4

' Asa=isi well: known to'those familiar with the art; many: materialshave. been. proposed. asaddiagents: to mineral. oils? for the? purposeof improving. the; oxidationcharaoteristics thereof. r'ornexamplaz incoperiolingapplication, Serial Ninnberflflflfi filedlDecember' 30,.1947;,by John Wo'Bronlmmo'w: U. Si Patent Number 2,571,332, werewerfeadiS'closedx the reaction products; of thiophenethiols'. and?phosphorus: halides; Although. these; reaction; products are eifective.an-

tioindants, even: when dispersed ina oili-they are disadvantageous from;the; standpoint of: solubilityi'immineral soil; Such" ;reactiomproductsare insohiblejininomevmineralwoils at! concentrations as; lowzasaabouta-Ol; weight percent. It will be apparent to those skilled in thevart I that the additive: will ber-dispersedrs theoil. The dis-'persioniwhichire'sultsisundesirable for lubricatinventionto provideoil-soluble antioxidant for jmineraloilsi. Another object is to. providea thiophenethiol phosphorusthalide reaction-prodnot having greatlyincreased 0i1-soll hility, An inglportantmbject to provide an.oil-soluble reaction. product; of, a. phosphorus -.halide, and an Ialiphatic. alcohol or an alkanethiol, and. a thin- 'phenethiol. Aenecific -objectfisz to provide. a mineral oil. containingcthis'reaction product. otheruobjects and advantages: of the presentinvention.will'ibecome, apparent to: thoseuek illedi in :1 I

thle'gartl jfronik the following detailed. description. Broadly;statedwthe, present invention-' rovides a mineral oil. containinganamount fsulficient :to

. improve the oxidation characteritic sr thereof of ajreaction. productobtained by reacting a monohydricr reactant .selcted fromthe group-consistingjiof alkanethiole having-between about 6. and abpntzecarbonatoms per mole'culeand aliphatic alcohols. having, between about;-6 and about 24 carbon/atoms.-

moleculeeandi.a t-phosphorus 55 2 halide;- ma-mol'ar oro'portion'varyingbetween oboe-505:1, respectively; and about 2.5l-;1',respeo1-tively, to produce an 'intermediateproduct,and reacting a'thiophenethioiwith the intermediate product msaz molar proportion. of: thiophen'ethioltoi'therpnosphorus. halide'rusedi to produce the: intermediate:productvaiwingbetween about 2.5:1, respectively; anvil about 0.521;respectively; the sum of the number offmolesiof themonohydric reactant:and:v of the thiophenethiohso reacted Withfeabh moleofphosphorushaliderbeing; three moles:

The: reactant reacted with the-phosphorus halide-reactant toiprepare theintermediateprod uctsofathis invention is. an.-"aliphatic alcohol or analkanethiol. Any aliphatic, monohydrica1:- coho'li l's'zntilizablehereimprovidedit has between about 16: and. about zercarbon atoms permolecule. The alcoholv molecule? can be branched-chain or straightchain,;saturated-or unsaturated. Likewise, thealc'ohol canrbeza primary;secondary, or tertiary: alcohoL- The primary alcohol however, is:preferred; Non-limiting examples 'of the aloehol neactantare n-hex-anol;nheptanol-l; meth ylhexan'ol-lg; 2-ethylhexanol- -l;. octanol-Z; 2-methylheptanol-Z h z-met-hyl octanol-Z; 2,6;dimethyl-3-methylo1heptane;decanol-l; dodecanoll ;-ner.ol geraniol 7 -ethyl-2-methylundecanol-ltetradecanol-l; hexadecanol-l octadeo- .anol-l oleyl v alc'0hol;-..linoleyl alcohol;v .linolenyl alcohol ;phytol; eicosanol-i; erucylalcohol; and

tetracosanol-l. M y y w v Thealkanethiol reactant shouldalso havebetween/about Sand: about 24; carbon atoms per molecule. As 11.; the.case of the alcohol reactant, the alkanethiol reactant: can bestraight-chain or {branched-chain. It is preferred that itbe a primarythiol, although a secondary oratertiary thiol-can be used. ,Non-limiting examples ofthe alkanethiol reactant are. hex-anethiol-l} octanethioll; de canethiol-lel dodcanethiol l; tetradecaneth-iol tg;hexadecganethiol- 11; oct'ad' ecanethiol li; 1 tertiary dodecariethioljftertiary tetradecanethiol;-- tertiary hexadecanethiol; eico-;SaHQliiilOh-Z; andtetraei'cosanethiol-l.

, The phosphorus' .halide reactants contemplated hereinincludethbhos'phor-iis' and'tii-halides and; derivatives thereof wherein twoof'the halogen atoms have been repneedby anonmetallic element. of group. VI'A of the periodic chart of the elements e, g, phosphorus-"oxyhalidesland phosphorus"- thiohalicles-.. The halogen atoms in thesecompounds-canbe-b-romine; chlorme, fluorine, or iodine:A-.combination.-of several halogena -can appear' imthe: same molecule;However, from the standpoint of commercial economics, it is preferred touse the phosphorus chlorides and bromides. Non-limiting examples of thephosphorus halide reactant are phosphorus pentabromide, phosphorustribromide, phosphorus monobromodichloride, phosphorusmonobromotetrachloride, phosphorus dibromotrichloride, phosphorusdibromotrifiuoride, phosphorus trichloride, phosphorus pentachloride,phosphorus dichlorotrifiuoride, phosphorus trifluoride, phosphoruspentafluoride, phosphorus triodide, phosphorus iodochloride, phosphorusoxybromide, phosphorus oxybromodichloride, phosphorus oxyfluoride,phosphorus oxychloride, phosphorus oxyiodide, phosphorus thiobromide,phosphorus thiobromodichloride, phosphorus thiochloride, phosphorusthiofiuoride, and phosphorus thioiodide.

In order to produce the intermediate product, the alcohol or thealkanethiol reactant is reacted with the phosphorus halide reactant in amolar proportion of between about 0.5:1, respectively, and about 2.5:1,respectively.

The reaction between the alcohol or alkanethiol reactant and thephosphorus halide reactant is an exothermic one. Accordingly, it isusually necessary to cool the reaction mixture during the initial stagesof the reaction. It is preferable to maintain the reactants at atemperature of between about C. and about C. during this initialreaction period. Then, the reaction mixture can be heated totemperatures as high as about 150 0., in order to complete the reaction.Often it is necessary to heat the reactants only to room temperature toachieve completion.

The time of the reaction is a non-critical factor. The completion of thereaction is usually indicated by a decrease in the formation of hydrogenhalide. Ordinarily, the reaction is complete in between about 3 hoursand about 10 hours.

The use of a solvent in the reaction is not essential. However, it isoften feasible to use a non-polar hydrocarbon solvent. Preferredsolvents are the aromatic hydrocarbon solvents of the benzene series,such as, for non-limiting examples, benzene, toluene, and xylene.

The hydrogen halide which is produced in the reaction can be removed bydriving it out with heat. However, it is preferable to use a hydrogenhalide acceptor for the purpose of removing the hydrogen halide. Suchacceptors, well known in the art, are usually tertiary amines, such as,by way of non-limiting examples, pyridine, tributylamine,amyldiethylamine, triamylamine, and the like.

The amine hydrohalide salts, thus produced, are insoluble in thereaction mixture. They can be removed therefrom by conventional'methods, such as by filtration or by decantation.

It must be strictly understood that the aliphatic alcohol orthealkanethiol reactant must be reacted with the phosphorus halide reactantfirst,

in order to produce final reaction products which are utilizable herein.The intermediate product can be 2-thiophenethiol or S-thiophenethiol, or

mixtures thereof. These compounds have been prepared by several methodswell known in the art. For example, B-thiophenethiol can be produced bythe methods described in copending application, Serial Number 721,454,filed January 10, 1947, now U. S. Patent Number 2,515,242; and in thearticle in Chem. Ind., 60, 593-5, 620 (1947) The preparation of2-thiophenethiol has been described in Ben, 19, 1615 (1886) and in Ber.,20, 1756 (1887).

The thiophenethiol reactant is reacted with the intermediate product ina molar proportion of thiophenethiol to the phosphorus halide used toproduce the intermediate product of between about 2.5:1, respectively,and about 0.521, respectively. In other words, the aliphatic alcohol oralkanethiol reactant and the phosphorus halide reactant and thethiophenethiol reactant are reacted, in accordance with this invention,in a molar proportion of between about 0.5:l:2.5, respectively, andabout 2.5:1:0.5, respectively. There is always a total of three moles ofalcohol or alkanethiol reactant and thiophenethiol reactant reacted witheach mole of phosphorus halide reactant. However, the reactants need notbe reacted only in unitary proportions, i. e., molecular proportionsneed not be 1 1 :2 or 2:1:1. There can be reacted fractional molecularquantities of reactants, e. g., 0.5:1:2.5, 1.5:1:1.5, 251120.49, etc.Accordingly, it will be obvious that the final reaction products of thisinvention are not pure compounds, but that they are complex mixtures ofcompounds. Therefore, it will be appreciated that any designationassigned to these reaction products other than .a recitation of theprocess for their preparation is not accurately descriptive of them.

The reaction between the intermediate product and the thiophenethiolreactant is also an exothermic reaction. Accordingly, the sameconditions of time and temperature as are used to produce theintermediate product are used in the reaction between the intermediateproduct and the thiophenethiol reactant. Likewise, similar manipulativesteps are involved. A solvent and/or a hydrogen halide acceptor can beused. Since these reaction conditions and manipulations have beendescribed hereinbefore, in conjunction with the discussion ofthe methodsof preparing the intermediate product, they will not be described againat this point. Reference, can be made to the aforementioned descriptionfor the details of the methods for producing the final reaction product.

The final reaction product, after being separated from the aminehydrohalid salt, can be further purified by distilling the reactionmixture to remove by-products and unreacted reactants. It is preferableto conduct such distillation under reduced pressure.

If desired, the reaction product can be waterwashed to removewater-soluble materials. Thereafter, it should be dried by any of thewell known techniques, such as, for example by use of a drying agent,like calcium chloride.

chloride to produce an intermediate product; and

further reacting this intermediate product with one-mole ofZ-thiophenethibl; inaccordance'witn the present invention. Qthercombinations arehexanoh- 1' (2:5) +phosphorus pentab-romide (-1 .0)'+2-thiophcnethiol 0.5); n-hepan'ol-l (l phosphorus tribromid'e(l-)-+-3--thiophenethiol (2;) 2-methyl heXan'oL-l- (1.75) +phosphorusmonobromodichloride (1.0) --|-3' thiophenethiol (1125) z ethylhexanoll-l(fi'.2'5) +phosphorus monobromotetrachloride (1.0) +2-thiophenethiol(:75); octanol-2' (0 ;52)'-{-phosphorus dibromotrich'loride(l.0)'+2-thiophenethiol (2. 48); 2 methylheptanol 2('2;07)+1:)hospliorus dibromo trifiuoride (1}.0)+3-thiophenethiol'(0.93); 2'- methyloctanol-2 (0'.8)-+ph'osphorus trichioride(1.0)+2-thiophenethi0l (2.2); 2-,0-dimethyl-3?-- methylolheptane (1.01)+phosphoruspentaclilo ride' (1.0)-+3-thioph'enethiol- (1 .99");decanol-l (0i6')'+.phosphorus dichlorotrifluoride (1.0)-+2-thiophenethiol (2 :4); dod'ecanol-2 1-.95')=+p-hos'- phorus trifiuoride(1.0) +3-thiophenethiol (1.05): nerol (2.2)-|-phosphorus pentafiuoride(1.0)+2- thiophenethiol (0.8); geraniol (1)+phosphorus triijodide(1)+3-:thiophenethiol (2); 7-ethyl-2- methylundecanol-l (2)+phosphorusiodochloride (1)+2 -thiophenethio1"(1); tetradecanol-l (1305)+phosp-horus oxybromide (1.0) +3-thioph'enethiol' (1195):; hexadecanol-1(1.2) +phos phorus oxybromodichloride '(-l.0)-+2-thi0phene' thiol (1.8);octadecanol-l' (0'.5)-{-phosphorus oxyfluoride (1.0) +3-thiophenethiol(2.5); oleyl alcohol (0.75) +phosphorus oxychloride (1.0) +2-thio'phenethiol (2.25); linoleyl. alcohol (2:51-1- phosphorus'oxyiodide: '(l'.0):+3$-.thiophenethioi (0:5); linolenyl alcohol.(0:5)-+phosphorus thiobromide (1.0)+2-thiophenethiot (2.5); phytol (0E8)+phosphorus thiochloride (1.0) +3-thiophene thiol (2.2); eico'sanol ll(1)-1-phosphorns. thiofluoride (1)+2-thiophensthioliv (2); erucylalcohol (0.6)+phosp-horus thioiodide (1) +3- thiophenethiol (2.4);tetracosanol-l (0.9) +phosphorustribromide (1.0) +2-thiophenethiol (2.1) hexanethiol-l (1.5)+p-hosphorus oxychloride (1.0)-( thiophenethiol(1.5) decanethiol-l (125)-l-phosphorus thiobromide(1.0)+2-thiophenethiol (1.75); dodecanethiol-l (:1)+phosphorusmonobromodichloride (1')+3-thioplienethiol (2); octanethiol-l(1.8)+phosphorus penta'chloride (1.0) +2-thiophenethiol (1.2);octad'eca'nethiol-l (0.5) +phoisphorus triiodide (1.0) 2"-thiophenethiol(2.5).

The following specific examples are for the purpose of illustrating themethods of preparing the reaction products of this invention, andofdemonstrating the advantages thereof. It must be strictly understoodthat this invention is not to be limited to th particular reactants andmolar proportions employed, or to the operations and manipulationsdescribed therein. A wide variety of other reactants and molarproportions, as set forth hereinbefore, can be used, as those skilled inthe art will readily understand.

EXAMPLE 1' H exadecano1-1 (1 -+phosphorus trichlorz'de- (1)+3-thiophenethiol (2) A mixtureiof 137 grams (1 mole) of phosphorustrichloride" and 25 cubic centimeters of benzene was placed in areaction vessel. To. thismixture was added, dropwise, a solution of242*gram's (1' mole) of hexadecanol-l in 450 cubic centimeters ofbenzene; over a period of 1.75 hours: During thistime, the temperatureofthe reaction mixture-wasma'intained at 2-5 G. Then, 237gra-ms WashedUnwashed Product: Product Percent Phosphorus.. 5.60v 5.94 Percent sulfur18.1. 18.0 Percent Chlorine 0.73 0.74

Solubility in mineral oili=l0.weight.pcrcent.

EXAMPLEIZ.

OctaclecanethioZ-I (1 phos;ph0rus trichloride (1 )+3-thioph'enethiol(2') To. 207 grams (1.5 moles) of phosphorus trichloride. was added. asolution of 286 grams (1. mole) oi octadecanethiolf-l' in. 200' gramsof'henzene', over aperiod of.- about. onefhourg. at a temperature. of2-4. C'. When addition was complete, the. coolant. wasremoved and thereaction mixture wasstirred'for 4 hours, at ambient temperature. Thebenzenev andthe excess phosphorus. trichloride wereremoved bydistillation. at 0., under 30 millimeters pressure. To the thus-topped.reactionv mixture were. added 25.0 cubic centimeters of'benzene and. 171 grams (2.2 moles) of pyridine- Then asolution of'232' grams (2' moles)of Bi-thiophenethioldh 250 cubic centimeters of benzene was added duringa'3'.hour period, with cooling,.at 2'.-5 C'.. After additionof. thereactants wascomplete, thereaction mixture wasstirredfor another.42151011178, t room temperature (about 25-30 'C.).,,and the. reactionproduct wasfiltered; The. filtrate wasv topped.at-"CZ under onemillimeter. pressure. Thev clear prod; uct decanted from the bottoms(79per cent yield) contained 5.04'per cent phosphorus. 311 112519 percent sulfur. It was soluble in mineral oil to an extent of 10 weightpercent.

EXAMPLE 3 Dodeca'nol- 1' (1.5) +phosphorus org/chloride (1)+.3-thiophenethiol(115) I To 153* grams (1 mole) ofphosphorusoxychloride"; 261* grams (323'- moles) of-pyridine; and-5'00 cubic:centimeters of benzene,- stirred at 2" CZ, were added 303' grams (15'moles) oi dodecanol l during a 3*-hourperiod; After being permitted tostand overnight at ambient temperatures, the reaction mixture was againcooled at 2 Cl Thereupon, 17 1-- grams (1.5 moles) of 3-thiophenethiolwere added, during'the courseof two hours. Then, the mixture was stirredat ambient temperatures for another 5 hours and filtered. Thefiltratewas-topped at (3., under 0.3 millimetenpressure, leaving 210 grams (40per cent yield) of reaction product. This reaction productcontained11.02'per cent phosphorus'and 10291 percent sulfur. It hasa three weightper cent solubility in mineral oil. I

EXAMPLE 4 Dodecanethz'oZ-1 (1) +phosphorus (1) +3-thzophenethiol (2) Toa mixture of 153 grams (1 mole) of phosphoru oxychloride, 261 grams (3.3moles) of pyridine, and 500 grams of benzene was added, dropwise, 218grams (1 mole) of dodecanethiol-l, at a reaction temperature of 2 C. Thereaction mixture stood overnight. Then, it was cooled to 2 C., while 232grams (2 moles) of 3-thiophenethiol were added during a 3-hour period.The reaction mixture was stirred, finally, at ambient temperatures for 4hours additional and then filtered. The filtrate was topped at 150 C.,and under 0.5 millimeter pressure. The residue was filtered yielding 405grams (82 per cent yield) of a reaction product containing 4.59 per centphosphorus and 33.09 per cent sulfur. It was soluble org chloride inmineral oil to the extent of three per cent, by

weight.

EXAMPLE 5 Dodecanethz'oZ-I (1)+phosphorus thiochloride(1)+3-thiophenethiol (2) (Method A) To a mixture of 260 grams (1.5moles) of phosphorus thiochloride and 100 grams (1.3 moles) of pyridine,were added 218 grams (1 mole) of dodecanethiol-l, over a period of onehour, at 2 C. Stirring was continued for 4 hours. At that time 250 cubiccentimeters of benzene were added, because the reaction mixture hadbecome very thick and viscous. After standing overnight, the mixture wasfiltered. The filterate was topped at 150 C., under 0.5 millimeterpressure. The bottoms from the distillation operation were diluted with500 cubic centimeters of benzene and 160 grams (2 moles) of pyridine.Then, 232 grams (2 moles) of 3-thiophenethiol were added, dropwise,during 2 hours, at 2 C. The mixture was then heated to 65 C., andstirred for 3 hours, with no additional heat being added. The resultingreaction mixture was filtered. The filtrate was topped at 120 C., under0.3 millimeter pressure, yielding 258 grams per cent yield) of product,which was decanted from a small quantity of a viscous material remainingin the bottom of the distillation flask. This product contained 3.97 percent phosphorus and 28.17 per cent of sulfur, and it was soluble inmineral oil to an r extent of 20 weight per cent.

EXAMPLE 6 Dodecanethiol-1 (1)+phosphorus thiochlorzde(1)-1-3-thz'ophenethiol (2) (Method B) To 170 grams (1 mole) ofphosphorus thiochloride, 500 grams of benzene, and 240 grams (3 moles)of pyridine, at 2 C., were added 218 grams (1 mole) of dodecanethiol-l.After being permitted to stand overnight, the mixture was cooled againto 2 0. Then, 232 grams (2 moles) of 3-thiophenethiol were added, over aperiod of 5 hours. The reaction mixture was filtered. The filtrate wastopped at 150 C. under 0.7 millimeter pressure, yielding 433 grams (85per cent) of a reaction product containing 5.80 per cent phosphorus and33.49 per cent sulfur. This reaction product was soluble in mineral oilto the extent of 5 weight per cent.

In order to determine the effect of these reaction products asantioxidants, they were subjected to a modified German tar test. In thistest, a 150 gram sample of a mineral oil containing the antioxidantunder test is maintained at 120 C. for 70 hours. Oxygen gas is bubbledthrough the test oil at the rate of two bubbles per second through a 6mm. (I. D.) inlet tube. for the duration of the test. The amount ofacidic oxidation products formed in this test is determined by titratingthe oil with alcoholic potassium hydroxide. This acidity is expressed interms of neutralization number (N. N.:number of mg. KOH equivalent toone gram of the oil blend). The results of testing oil blends of theaforedescribed reaction products are set forth in Table 1.

The test oil used was a highly-refined oil, suitable for use intransformers, which was prepared by treating coastal distillate stockwith 40 pounds of 98 per cent sulfuric acid and 180 pounds of 103 percent oleum per barrel, and then percolating the acid-treated oil throughclay. This oil had a specific gravity of 0.871, a flash point of 310 F.,and a Saybolt Universal viscosity of 69 seconds at F. Such an oil formsacidic products upon oxidation, as is indicated by a high N. N.

TABLE 1 Gone. in Test Product of Example Gil, Results,

Percent N. N.

18. 0 O. 1 0.05 '0. 1 0. O2 0. 1 1. 2 0. l 0. 1

' when subjected to high temperatures. The products thus formed arecorrosive to metal-alloy bearings, such as cadmium-silver bearings, andmay cause bearing failure within a relatively short period of time.

Oil blends of the reaction products of the specific illustrativeexamples were tested in the following test, to determine thecharacteristics thereof with respect to bearing corrosion: A carefullyweighed, 6 gram section of a cadmium-silver alloy surfaced bearing isplaced in a sample of the test oil. The oil is maintained at C., for 22hours, while air is bubbled against the surface of the bearing at therate of two liters per hour. Then, the bearing is carefully reweighed.The loss in weight of the bearing affords a measure of the corrosivenessof the oil under test. The oil used herein was a blend of Pennsylvanianeutral stock and Pennsylvania residuum stock, each of which stocks hadbeen refined with bis-fi-chloroethyl ether (Chlorex), having a specificgravity of 0.872, a flash point of 435 F., and a Saybolt Universalviscosity of 318 seconds at 100 F. This oil is an S. A. E. #20 grademotor oil. Test results of blends of additives in this oil are recordedin Table 2.

TABLE 2 Gone. in Product of Example Bearmg Percent 20 l 2 Nil 3 3 Nil Inview of the foregoing, it will be apparent that the reaction products ofthis invention are effective in several ways. They are quite soluble in.mineral-foil. Theoxidati'oirstabil'ity-of. mineral.

thereby. also; bearing-corrosion isvmaterially reduced when "these.products are added to motor-oils; The additives of invention; :are alsouseful oxidation stabilizers tor. rubber "and the lilies.

The amounts of. the reaction products of. this invmtion which areeffective to improve. the oxidation stability mineral oils variesdependent-.nn the particular reaction product used and.- cn the oil tobe improved. Invgerrerahthe amount or reaction :productuse'd: will varybetween about 0105* per cent and about =10: per cent, by weight.Preferably, between. about 0.1. and about 2 per centisisused...

Mineral oil concentratesare also-contemplated. in-this invention, suchconcentrates-containing substantially larger amounts of. theantioridantv than, set iorth hereinbetore. Thus, relatively lage'amounts, i. e., upwards of about. tenper centbyweight and. up toabout 49 per cent can be incorporated in an 011i fraction. The oil con.-centrates. thus obtained may thereafter be diluted with. ,a suitablequantity of mineral-oil prior to. use, to produce a mineral oilcomposition containing the-desired optimum concentrationof the additive.

- ilt'is-tobe understoodthat, in addition to the additive of the presentinvention, otheroiladdition agents can be incorporated. in the oil com.-position. Such additives include, for example,

additives, oiliness agents, pour pcintdepressantsyantirust agents,detergents, etc.

- Although the present invention. has been described with. preferredembodimentaitis to be understood that modifications and variations maybe resorted to without departing from the spirit and scope thereof,. asthose skilled in the art will readily understand. Such variations andmodifications are considered to be within the purview and "scope of theappended claims.

.;What is claimed is;

=1.-A mineral. lubricatingv oil containing an amount sufficient toimprove the oxidation characteristics thereof of the reaction productobtained by reacting almonoh-ydric reactant. selected from th groupconsisting of alkanethiols having between about '6 and about 2 L carbonatoms per molecule and aliphatic alcohols having. between. about 6 andabout-24 carbon atomsper molecule,

and a phosphorus halide, in a molar proportion varyingbetween about(1.521., respectively, and about 2.521, respective-moat a temperature ofbetween about 'C. and about 150 (1., and for between about 3- hours andabout lohours, to produce uni-intermediate product, and reacting .athiophenethiol with-said intermediate product, in a molar proportion ofsaid thiophenethiol to said phosphorushalide used to produce saidintermediate product varying between about 2.5:1, respcctively,..andabout 0.511, respectively, at a temperature of between about ll C. andabout 150 C., and forbetween about 3 hours "and about 10 hours';the sumof the number of moles 'of said monohydric reactant and of saidthiophcncthiol so'frea'cted with each moleof said phosphorus halidebeing. three moles.

2. A mineral lubricating oil containing between about 0.01 per cent andabout 10 per cent, by weight, of the reaction product obtained byreacting a monohydric reactant selected from the group consisting ofalkanethiols having between about 6 and about 24 carbon atoms permolecule and aliphatic alcohols having between about 6 and about 24carbon atoms per molecule, and a iii phosphorus halide, in a molarproportion varying:

between about-0.5: 1, respectively, and about 2.5: 1, respectively, ata, temperature of between about 0* C. and. about 6., and for betweenabout 3 hourss 'and about ltlheurs, to produce-anintermediate product,and reacting a. thiophenethiolwith saidintermed-iate product, a molarpro;- portionof said thiophenethiol tosaid phosphorus halideused: toproduce said intermediate product varying between. about 2.5:1,respectively, and about 0.511, respectively, at a temperature of be--tween about 0" C; and about 1-50 C., and, for bee;

tween about 3' hours and; about 10 hours; the sum. or the number ofmolesof: said monohydric. re actant and: of said.thiophenethiolsoreacted with each melee-f. said phosphorus halide beingthree: moles.

I 3, A mineral lubricating oil containing an. amount sufficient toimprove the oxidation characteristics. thereof. attire reaction productobtained by reacting a. monohydric reactant selooted tromthe groupconsisting. oi alkaneth-iols having. between about. 6. and about 24.carbon atoms per molecule and aliphatic alcohols hav ing-between about Sand about 24 carbon atoms per molecule-and phosphorus trichloride. in a.molar proportion. varying between about 0.5-:1, respectively, and. about25:1,. respectively, at a. temperature of between. about 9 C. and. about150 C. and for between about 3 hours and about it hours, to produceanintermediate product, and reacting a thiophenethiol withsaidintermediate: product, in a molar proportion of. saidthi-ophenethiol to said, phosphorus. trichloride used. to produce saidintermediate product varybetweenabout 2.5:1, respectively, and. about(idol, respectively, at a temperature of between. about 0 C. and. about1-50 (3., and for between: about3 hours and: aboutlO hours; the sum of.the. number of moles of said monohydric. reactant and of saidthiophenethiol so reacted witheachmole of said phosphorus trich-loridebeing three moles.

1. A. mineral lubricating oil containingan amount suflicient toimprove.- the oxidation Q1131. acteristics thereof of the: reactionproduct obtained by reacting a monohydric reactant selected from. thegroup consisting of 'alkanethiols' having between about 6 and about atcarbon atoms permolecule and aliphatic alcohols having between. about 6and about 24 carbon atoms per molecule, and phosphorus oxychloride, in amolar proportionvarying between about 9.521,. respectively, and about2.5 :.1,. respectively, atv a temperatureof between about 0 C. and about150 0., and for between about '3 hoursv and about 10 hours, toproduceintermediate product, and reacting a thiophenethiol with saidintermediateproduct, in amolar proportion of said thiophenethiol to saidphosphorus oxychloride used to produce said intermediate product varyingbetween about 2.5:1, respectively, and about 0.5:1, respectively, at atemperature between about 0- C. and about l5 C., and for between about 3hours about 1-0- hours; the sum of the number of moles of saidmonohydric reactant and of said thicphenethiol so reacted with eachmole. of said phosphorus oxyehloride being three moles.

5. A mineral lubricating oil containing an amount sufficient to improvethe oxidation characteristics thereof of the reaction product obtainedby reacting a monohydric reactant selected from the group consisting ofalkanethiols having between about 6 and about 24 carbon atoms permolecule and aliphatic alcohols having between about 6 and about 24carbon atoms per molecule, and phosphorus thiochloride, in a molarproportion varying between about 0.521, respectively, and about 2.5:1,respectively, at a temperature of between about C. and about 150 C., andfor between about 3 hours and about hours, to produce an intermediateproduct, and reacting a thiophenethiol with said intermediate product,in a molar proportion of said thiophenethiol to said phosphorusthiochloride used to produce said intermediate product varying betweenabout 2.5:1, respectively, and about 0.5:1, respectively, at atemperature of between about 0 C. and about 150 C., and for betweenabout 3 hours and about 10 hours, the sum of the number of moles of saidmonohydric reactant and of said thiophenethiol so reacted with each moleof said phosphorus thiochloride being three moles.

6. A mineral lubricating oil containing an amount sufiicient to improvethe oxidation characteristics thereof of the reaction product obtainedby reacting an alkanethiol having between about 6 and about 24 carbonatoms per molecule, and a phosphorus chloride, in a molar proportionvarying between about 0.511, respectively, and about 2.5:1,respectively, at a temperature of be tween about 0 C. and about 150 C.,and for between about 3 hours and about 10 hours, to produce anintermediate product, and reacting a thiophenethiol with saidintermediate product, in a molar proportion of said thiophenethiol tosaid phosphorus chloride used to produce said intermediate productvarying between about 2.511, respectively, and about 0.5:1,respectively, at a temperature of between about 0 C. and about 150 C.,and for between about 3 hours and about 10 hours, the sum of the numberof moles of said alkanethiol and of said thiophenethiol so reacted witheach mole of said phosphorus chloride being three moles.

'7. A mineral lubricating oil containing an' amount suflicient toimprove the oxidation characteristics thereof of the reaction productobtained by reacting an aliphatic alcohol having between about 6 andabout 24 carbon atoms per molecule, and a phosphorus chloride, in amolar proportion varying between about 0.5:1, respectively, and about2.5:1, respectively, at a temperature of between about 0 C. and about150 C. and for between about 3 hours and about 10 hours, to produce anintermediate product, and reacting a thiophenethiol with saidintermediate product, in a molar proportion of said thiophenethiol tosaid phosphorus chloride used to produce said intermediate productvarying between about 2.5:1, respectively, and about 0.5:1,respectively, at a temperature of between about 0 C. and about 150 C.,and for between about 1 3 hoursand about 10 hours; the sum of the numberof moles of said aliphatic alcohol and of said thiophenethiol so reactedwith each mole of said -phosphorus chloride being three moles.

tween about 0.5:1, respectively, and about 2.511, respectively, at atemperature of between about 0 C. and about C., and for between about 3hours and about 10 hours, to produce an intermediate product, andreacting 3-thiophenethiol with said intermediate product, in a molarproportion of said 3-thiophenethiol to said phosphorus thiochloride usedto produce said intermediate product varying between about 2.5: 1,respectively, and about 0.521, respectively, at a temperature of betweenabout 0 C. and about 150 C., and for between about 3 hours and about 10hours; the sum of the number of moles of said dodecanethiol and of saidB-thiophenethiol so reacted with each mole of said phosphorusthiochloride being three moles.

9. A mineral lubricating oil containing an amount sufiicient to improvethe oxidation characteristics thereof of the reaction product obtainedby reacting dodecanol and phosphorus oxychloride, in a molar proportionvarying between about 0.5:1, respectively, and about 2.5:1,respectively, at a temperature of between about 0 C. and about 150 C.,and for between about 3 hours and about 10 hours, to produce anintermediate product, and reacting 3-thiophenethiol with saidintermediate product, in a molar proportion of said 3-thiophenethio1 tosaid phosphorus oxychloride used to produce said intermediate productvarying between about 2.5:1, respectively, and about 0.5:1,respectively, at a temperature of between about 0 C. and about 150 C.,and for between about 3 hours and about 10 hours; the sum of the numberof moles of said dodecanol and of said 3-thiophenethiol so reacted witheach mole of said phosphorus oxychloride being three moles.

10. A mineral lubricating oil containing an amount sufficient to improvethe oxidation characteristics thereof of the reaction product obtainedby reacting hexadecanol and phosphorus trichloride, in a molarproportion varying between about 0.511, respectively, and about 2.5:1,respectively, at a temperature of between about 0 C. and about 150 C.,and for between about 3 hours and about 10 hours, to produce anintermediate product, and reacting 3-thiophenethiol with saidintermediate product, in a molar proportion of said 3-thiophenethiol tosaid phosphorus trichloride used to produce said intermediate productvarying between about 2.5:1, respectively, and about 0.5:1,respectively, at a temperature of between about 0 C. and about 150 C.,and for between about 3 hours and about 10 hours; the sum of the numberof moles-of said hexadecanol and of said 3-thiophenethiol so reactedwith each mole of said phosphorus trichloride being three moles.

JOSEPH J. WEI-IRLE.

Reierences Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,495,467 Morris et a1 Jan. 24, 1950 2,500,498 Reiff et alMar. 14, 1950 2,502,390 Reifi et a1 Mar. 28, 1950

1. A MINERAL LUBRICATING OIL CONTAINING AN AMOUNT SUFFICIENT TO IMPROVETHE OXIDATION CHARACTERISTICS THEREOF OF THE REACTION PRODUCT OBTAINEDBY REACTING A MONOHYDRIC REACTANT SELECTED FROM THE GROUP CONSISTING OFALKANETHIOLS HAVING BETWEEN ABOUT 6 AND ABOUT 24 CARBON ATOMS PERMOLECULE AND ALIPHATIC ALCOHOLS HAVING BETWEEN ABOUT 6 AND ABOUT 24CARBON ATOMS PER MOLECULE AND A PHOSPHORUS HALIDE, IN A MOLAR PROPORTIONVARYING BETWEEN ABOUT 0.5:1, RESPECTIVELY AND ABOUT 2.5:1, RESPECTIVELY,AT A TEMPERATURE OF BETWEEN ABOUT 0* C. AND ABOUT 150* C., AND FORBETWEEN ABOUT 3 HOURS AND ABOUT 10 HOURS, TO PRODUCE AN INTERMEDIATEPRODUCT, AND REACTING A THIOPHENETHIOL WITH SAID INTERMEDIATE PRODUCT,IN A MOLAR PROPORTION OF SAID THIOPHENETHIOL TO SAID PHOSPHORUS HALIDEUSED TO PRODUCE SAID INTERMEDIATE PRODUCT VARYING BETWEEN ABOUT 2.5:1,RESPECTIVELY, AND ABOUT 0.5:1, RESPECTIVELY, AT A TEMPERATURE OF BETWEENABOUT 0* C. AND ABOUT 150* C., AND FOR BETWEEN ABOUT 3 HOURS AND ABOUT10 HOURS; THE SUM OF THE NUMBER OF MOLES OF SAID MONOHYDRIC REACTANT ANDOF SAID THIOPHENETHIOL SO REACTED WITH EACH MOLE OF SAID PHOSPHORUSHALIDE BEING THREE MOLES.